Efficient tandem reactions on a single catalytic nanostructure would be beneficial to improving chemical transformation efficiency and reducing safety implications. It is imperative to identify the active sites for ea...Efficient tandem reactions on a single catalytic nanostructure would be beneficial to improving chemical transformation efficiency and reducing safety implications. It is imperative to identify the active sites for each single step reaction so that the entire reaction process can be optimized by designing and integrating the sites. Herein, hydrogen transfer reaction is taken as a proof-of-concept demonstration to show that the spatial integration of active sites is important to the catalytic efficiency of the entire process in tandem reactions. We identified specific active sites (i.e., various sites at faces versus corners and edges) for formic acid decomposition and alkene/nitrobenzene hydrogenation-the two steps in hydrogen transfer reactions, by employing three different shapes of Pd nanocrystals in tunable sizes. The investigation reveals that the decomposition of formic acid occurs preferentially at the edge sites of cubic nanocrystal and the plane sites of octahedral/ tetrahedral nanocrystals, while the hydrogenation takes place mainly at the edge sites of both cubic and octahedral/ tetrahedral nanocrystals. The consistency of active edge sites during different step reactions enables cubic nanocrystals to exhibit a higher activity than octahedral nanocrystals in hydrogen transfer reactions, although octahedrons offer comparable activities to cubes in formic acid decomposition and hydrogenation reactions. Guided by these findings, we further improved the overall performance of tandem catalysis by specifically promoting the limiting step through nanocatalyst design. This work provides insights into the rational design of heterogeneous nanocatalysts in tandem reactions.展开更多
A highly efficient and reusable plane‐curved and interlayer‐expanded MoS2nanocatalyst with increased exposure of active sites was prepared.The catalyst was used for the heterogeneous hydrogen transfer reaction of ni...A highly efficient and reusable plane‐curved and interlayer‐expanded MoS2nanocatalyst with increased exposure of active sites was prepared.The catalyst was used for the heterogeneous hydrogen transfer reaction of nitroarenes with hydrazine monohydrate as a reductant under mild reaction conditions without pressure and base,which was different from other hydrogen transfer systems that require the presence of a base(e.g.,propan‐2‐ol/KOH).The sandwiching of carbon between the MoS2nanosheets increased the distance between the layers of MoS2and exposed more Mo sites,resulting in superior catalytic performance compared with that of bulk MoS2catalyst.The active hydrogen(H*)generated from N2H4could directly transfer to the–NO2groups of nitrobenzene to form aniline followed by N2emission,which was confirmed by detecting the gas emission with mass spectrometry during the decomposition of hydrazine or the co‐existence of nitrobenzene and hydrazine.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.展开更多
A series of heteropolytungstates has been synthesized and utilized as catalysts to catalyze oxidation of benzyl alcohol with aqueous hydrogen peroxide. The results indicated that three of these catalysts showed the pr...A series of heteropolytungstates has been synthesized and utilized as catalysts to catalyze oxidation of benzyl alcohol with aqueous hydrogen peroxide. The results indicated that three of these catalysts showed the properties of reaction-controlled phasetransfer catalysis, and they had excellent catalytic ability to the oxidation of benzyl alcohol. No other by-products were detected by gas chromatography. Once the hydrogen peroxide was consumed completely, the catalyst precipitated from solvent, and the results of the catalyst recycle showed that the catalyst had high stability.展开更多
Searching alternatives to Pt-based catalyst for producing hydrogen via water splitting has gathered enormous attention to develop renewable energy. Phosphorene has been investigated widely for its large surface area, ...Searching alternatives to Pt-based catalyst for producing hydrogen via water splitting has gathered enormous attention to develop renewable energy. Phosphorene has been investigated widely for its large surface area, low cost, and high carrier mobility, however, the poor activity in hydrogen evolution reaction (HER) and low conductivity limit its practical application. Herein, on the basis of first-principles calculations, we demonstrate that the catalytic HER in phosphorene can be enhanced significantly with cobalt intercalations. The Co-intercalated phosphorene is metallic with charge transfer from Co atoms to phosphorene, which could enhance the catalytic activity of phosphorene. In addition, the calculated Gibbs free energy of hydrogen adsorption on Co-intercalated phosphorene bilayer is comparable to that on Pt(111) surface, independent of the degree of hydrogen coverage. Our study implies that the Co intercalation provides an effective approach to enhance the catalytic HER in phosphorene.展开更多
Hydrided Mg-3Ni-2MnO2 composite powders were fabricated by reactive ball milling with hydrogen, and accumulative hydrogenation kinetics and temperature field of reaction bed with various porosities (0.37, 0.53 and 0.6...Hydrided Mg-3Ni-2MnO2 composite powders were fabricated by reactive ball milling with hydrogen, and accumulative hydrogenation kinetics and temperature field of reaction bed with various porosities (0.37, 0.53 and 0.63) were measured. The results show that the accumulative hydrogenation kinetics of Mg-3Ni-2MnO2 powder reaction bed depends strongly on the effect of heat transfer, mass transfer and intrinsic reaction together. The reaction bed with the porosity of 0.53 exhibits the largest hydrogenation rate. During the hydrogenation process, the temperature of reaction bed rises quickly due to the fast release of heat, and the temperature difference between center and wall with 0.53 porosity can keep high even for a long time, which promotes fast heat transfer. The further analysis indicates that more emphases should be put on heat transfer rate rather than the only improvement of the effective thermal conductivity.展开更多
The methanol to olefins （MTO） reaction was performed over ZSM‐5 zeolite at 300℃ under various methanol weight hourly space velocity （WHSV） values. During these trials, the catalytic perfor‐mance was assessed, i...The methanol to olefins （MTO） reaction was performed over ZSM‐5 zeolite at 300℃ under various methanol weight hourly space velocity （WHSV） values. During these trials, the catalytic perfor‐mance was assessed, in addition to the formation and function of organic compounds retained in the zeolite. Analysis of reaction effluents and confined organics demonstrated a dual‐cycle reaction mechanism when employing ZSM‐5. The extent of the hydrogen transfer reaction, a secondary reac‐tion in the MTO process, varied as the catalyst‐methanol contact time was changed. In addition, 12C/13C‐methanol switch experiments indicated a relationship between the dual‐cycle mechanism and the extent of the hydrogen transfer reaction. Reactions employing a low methanol WHSV in conjunction with a long contact time favored the hydrogen transfer reaction to give alkene products and promoted the generation and accumulation of retained organic species, such as aromatics and methylcyclopentadienes, which enhance the aromatic cycle. When using higher WHSV values, the reduced contact times lessened the extent of the hydrogen transfer reaction and limited the genera‐tion of methylcyclopentadienes and aromatic species. This suppressed the aromatic cycle, such that the alkene cycle became the dominant route during the MTO reaction.展开更多
The asymmetric nitro-Mannich reaction is one of the traditional methods for forming carbon-carbon bond. By this reaction, the corresponding products with two contiguous stereocenters containing nitrogen substituents c...The asymmetric nitro-Mannich reaction is one of the traditional methods for forming carbon-carbon bond. By this reaction, the corresponding products with two contiguous stereocenters containing nitrogen substituents can be obtained. These β-nitro amine products can be easily transformed into 1,2-diamines by reduction of the corresponding nitro groups by means of the Nef reaction. It is well known that chiral 1,2-diamines Nay an important role in many fields.展开更多
基金financially supported in part by the National Key R&D Program of China(2017YFA0207301)the Nation Natural Science Foundation of China(21725102,U1832156,21601173,21890751 and 21803002)+4 种基金CAS Key Research Program of Frontier Sciences(QYZDB-SSW-SLH018)CAS Interdisciplinary Innovation Teamthe Ministry of Science and Technology of China(2016YFA0200602 and 2018YFA0208603)the Chinese Universities Scientific Fund(WK2310000067)the support from USTC Center for the Micro- and Nanoscale Research and Fabrication
文摘Efficient tandem reactions on a single catalytic nanostructure would be beneficial to improving chemical transformation efficiency and reducing safety implications. It is imperative to identify the active sites for each single step reaction so that the entire reaction process can be optimized by designing and integrating the sites. Herein, hydrogen transfer reaction is taken as a proof-of-concept demonstration to show that the spatial integration of active sites is important to the catalytic efficiency of the entire process in tandem reactions. We identified specific active sites (i.e., various sites at faces versus corners and edges) for formic acid decomposition and alkene/nitrobenzene hydrogenation-the two steps in hydrogen transfer reactions, by employing three different shapes of Pd nanocrystals in tunable sizes. The investigation reveals that the decomposition of formic acid occurs preferentially at the edge sites of cubic nanocrystal and the plane sites of octahedral/ tetrahedral nanocrystals, while the hydrogenation takes place mainly at the edge sites of both cubic and octahedral/ tetrahedral nanocrystals. The consistency of active edge sites during different step reactions enables cubic nanocrystals to exhibit a higher activity than octahedral nanocrystals in hydrogen transfer reactions, although octahedrons offer comparable activities to cubes in formic acid decomposition and hydrogenation reactions. Guided by these findings, we further improved the overall performance of tandem catalysis by specifically promoting the limiting step through nanocatalyst design. This work provides insights into the rational design of heterogeneous nanocatalysts in tandem reactions.
基金supported by the Ministry of Science and Technology(MOST,2016YFA0204100 and 2011CBA00504)the National Natural Science Foundation of China(21573254,91545110)+1 种基金the Youth Innovation Promotion Association(CAS)the Sinopec China~~
文摘A highly efficient and reusable plane‐curved and interlayer‐expanded MoS2nanocatalyst with increased exposure of active sites was prepared.The catalyst was used for the heterogeneous hydrogen transfer reaction of nitroarenes with hydrazine monohydrate as a reductant under mild reaction conditions without pressure and base,which was different from other hydrogen transfer systems that require the presence of a base(e.g.,propan‐2‐ol/KOH).The sandwiching of carbon between the MoS2nanosheets increased the distance between the layers of MoS2and exposed more Mo sites,resulting in superior catalytic performance compared with that of bulk MoS2catalyst.The active hydrogen(H*)generated from N2H4could directly transfer to the–NO2groups of nitrobenzene to form aniline followed by N2emission,which was confirmed by detecting the gas emission with mass spectrometry during the decomposition of hydrazine or the co‐existence of nitrobenzene and hydrazine.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.
文摘A series of heteropolytungstates has been synthesized and utilized as catalysts to catalyze oxidation of benzyl alcohol with aqueous hydrogen peroxide. The results indicated that three of these catalysts showed the properties of reaction-controlled phasetransfer catalysis, and they had excellent catalytic ability to the oxidation of benzyl alcohol. No other by-products were detected by gas chromatography. Once the hydrogen peroxide was consumed completely, the catalyst precipitated from solvent, and the results of the catalyst recycle showed that the catalyst had high stability.
基金the National Natural Science Foundation of China (No.21573204 and No.21421063)Ministry of Science and Technology of China (2018YFA0208603 and 2016YFA0200602)Anhui Initiative in Quantum Information Technologies, the Fundamental Research Funds for the Central UniversitiesUniversities, the National Program for Support of Top-notch Young Professional, Chinese Academy of Sciences Interdisciplinary Innovation Team, and Super Computer Center of USTC supercomputing center and CAS supercomputing center.
文摘Searching alternatives to Pt-based catalyst for producing hydrogen via water splitting has gathered enormous attention to develop renewable energy. Phosphorene has been investigated widely for its large surface area, low cost, and high carrier mobility, however, the poor activity in hydrogen evolution reaction (HER) and low conductivity limit its practical application. Herein, on the basis of first-principles calculations, we demonstrate that the catalytic HER in phosphorene can be enhanced significantly with cobalt intercalations. The Co-intercalated phosphorene is metallic with charge transfer from Co atoms to phosphorene, which could enhance the catalytic activity of phosphorene. In addition, the calculated Gibbs free energy of hydrogen adsorption on Co-intercalated phosphorene bilayer is comparable to that on Pt(111) surface, independent of the degree of hydrogen coverage. Our study implies that the Co intercalation provides an effective approach to enhance the catalytic HER in phosphorene.
基金Projects(2006126, 2006130 and 2008GG10007004) supported by the Science & Technology Plan of Shandong Province, China
文摘Hydrided Mg-3Ni-2MnO2 composite powders were fabricated by reactive ball milling with hydrogen, and accumulative hydrogenation kinetics and temperature field of reaction bed with various porosities (0.37, 0.53 and 0.63) were measured. The results show that the accumulative hydrogenation kinetics of Mg-3Ni-2MnO2 powder reaction bed depends strongly on the effect of heat transfer, mass transfer and intrinsic reaction together. The reaction bed with the porosity of 0.53 exhibits the largest hydrogenation rate. During the hydrogenation process, the temperature of reaction bed rises quickly due to the fast release of heat, and the temperature difference between center and wall with 0.53 porosity can keep high even for a long time, which promotes fast heat transfer. The further analysis indicates that more emphases should be put on heat transfer rate rather than the only improvement of the effective thermal conductivity.
基金supported by the National Natural Science Foundation of China (91545104,21576256,21473182,21273230,21273005)the Youth Innovation Promotion Association of the Chinese Academy of Sciences~~
文摘The methanol to olefins （MTO） reaction was performed over ZSM‐5 zeolite at 300℃ under various methanol weight hourly space velocity （WHSV） values. During these trials, the catalytic perfor‐mance was assessed, in addition to the formation and function of organic compounds retained in the zeolite. Analysis of reaction effluents and confined organics demonstrated a dual‐cycle reaction mechanism when employing ZSM‐5. The extent of the hydrogen transfer reaction, a secondary reac‐tion in the MTO process, varied as the catalyst‐methanol contact time was changed. In addition, 12C/13C‐methanol switch experiments indicated a relationship between the dual‐cycle mechanism and the extent of the hydrogen transfer reaction. Reactions employing a low methanol WHSV in conjunction with a long contact time favored the hydrogen transfer reaction to give alkene products and promoted the generation and accumulation of retained organic species, such as aromatics and methylcyclopentadienes, which enhance the aromatic cycle. When using higher WHSV values, the reduced contact times lessened the extent of the hydrogen transfer reaction and limited the genera‐tion of methylcyclopentadienes and aromatic species. This suppressed the aromatic cycle, such that the alkene cycle became the dominant route during the MTO reaction.
基金Supported by the National Natural Science Foundation of China（No. 51373067）.
文摘The asymmetric nitro-Mannich reaction is one of the traditional methods for forming carbon-carbon bond. By this reaction, the corresponding products with two contiguous stereocenters containing nitrogen substituents can be obtained. These β-nitro amine products can be easily transformed into 1,2-diamines by reduction of the corresponding nitro groups by means of the Nef reaction. It is well known that chiral 1,2-diamines Nay an important role in many fields.
